Avenging Spider-man #16 p. 13

Shortly after the apparent death of Doctor Octopus, Spider-man revamped himself as the Superior Spider-man while taking on a much more aggressive approach to situations. While teaming up with the X-men, this caused him to come into conflict with Wolverine and leading Superior Spider-man to put him in his place.

Nice page of Spider-Ock taking down Wolverine and an early appearance of Superior Spider-man from what I recall (I think his 3rd overall as Superior officially).